Hydroxyethyl-azole derivatives

ABSTRACT

Hydroxyethyl-azole derivatives of the formula ##STR1## in which R 1  represents alkyl or the grouping Ar--Y--, 
     Ar represents optionally substituted aryl, 
     X represents a nitrogen atom or the CH group, 
     Y represents a direct bond or the grouping --CH 2  --, --CH 2  CH 2  --, --OCH 2  --, --SCH 2  --, --CH═CH-- or --C.tbd.C--, 
     Z represents oxygen or the NOR 2  group and 
     R 2  represents hydrogen, alkyl, alkenyl, alkynyl, optionally substituted aralkyl or optionally substituted cycloalkylalkyl, 
     or addition products thereof with acids or metal salts, which possess fungicidal activity.

This is a division, of application Ser. No. 650,965, filed Sept. 14,1984, now U.S. Pat. No. 4,645,767.

The present invention relates to new hydroxyethylazole derivatives,several processes for their preparation and their use as fungicides.

It has already been disclosed that certain hydroxyethyl-azolederivatives, such as, for example,1-(2,4-dichlorophenoxy)-3,3-dimethyl-2-(1,2,4-triazol-1-yl-methyl)-2-butanolor 1-(4-chlorophenoxy)-3,3-dimethyl-2-(imidazol-1-yl)-2-butanol, havefungicidal properties (compare European No. 0,040,345 corresponding toU.S. application Ser. No. 499,679 filed June 6, 1983, now U.S. Pat. No.4,532,341.) However, the effectiveness of these compounds is not alwayscompletely satisfactory, especially when low amounts and concentrationare applied.

New hydroxyethyl-azole derivatives of the general formula (I) ##STR2##in which R¹ represents alkyl or the grouping Ar--Y--,

Ar represents optionally substituted aryl,

X represents a nitrogen atom or the CH group,

Y represents a direct bond or the grouping --CH₂ --, --CH₂ CH₂ --,--OCH₂ --, --SCH₂ --, --CH═CH-- or --C.tbd.C--,

Z represents oxygen or the NOR² group and

R² represents hydrogen, alkyl, alkenyl, alkinyl, optionally substitutedaralkyl or optionally substituted cycloalkylalkyl,

and acid addition salts and metal salt complexes thereof, have now beenfound.

It has furthermore been found that the hydroxyethyl-azole derivatives ofthe formula (I) are obtained when

(a) hydroxyethylazolyl-acetal derivatives of the formula (II) ##STR3##in which Z¹ and Z² represent alkyl or, together with the oxygen atom towhich they are bonded, represent a dioxolane ring; and

R¹ and X have the abovementioned meaning, are heated in the presence ofa mixture of water and an organic solvent and in the presence of anacid; and/or

(b) the hydroxyethyl-azole derivatives, obtained by process (a), of theformula (Ia) ##STR4## in which R¹ and X have the abovementioned meaning,or the hydroxyethylazolyl-acetal derivatives of the formula (II) arereacted with hydroxylamine derivatives of the formula (III)

    H.sub.2 N--O--R.sup.2                                      (III)

in which

R² has the abovementioned meaning, in the presence of a diluent; or

(c) the hydroxyethyl-azole derivatives, obtained by process (b), of theformula (Ib) (that is to say those compounds of the formula (I) in whichZ represents the NOH group) ##STR5## in which R¹ and X have theabovementioned meaning, are reacted with halides of the formula (IV)

    Hal--R.sup.3                                               (IV)

in which

Hal represents chlorine, bromine or iodine and

R³ represents the meanings of R², with the exception of hydrogen,

in the presence of a diluent and if appropriate in the presence of abase; or

(d) oxiranes of the formula (V) ##STR6## in which R¹ and R³ have theabovementioned meanings, are reacted with azoles of the formula (VI)##STR7## in which M represents hydrogen or an alkali metal, in thepresence of a diluent and if appropriate in the presence of a base.

If appropriate, an acid or a metal salt can then be added on to thecompounds of the formula (I) thus obtained.

The new hydroxyethyl-azole derivatives of the formula (I) have powerfulfungicidal properties. Surprisingly, the compounds according to theinvention exhibit a more powerful action than the hydroxyethyl-azolederivatives1-(2,4-dichlorophenoxy)-3,3-dimethyl-2-(1,2,4-triazole-1-yl-methyl)-2-butanoland 1-(4-chlorophenoxy)-3,3-dimethyl-2-(imidazol-1-yl)-2-butanol, whichare known from the prior art and are closely related compoundsstructurally and from the point of view of their action. The substancesaccording to the invention thus represent an enrichment of the art.

Formula (I) provides a general definition of the hydroxyethyl-azolederivatives according to the invention. Preferably, in this formula,

R¹ represents straight-chain or branched alkyl with 1 to 6 carbon atomsor the grouping Ar--Y;

Ar represents naphthyl, or represents phenyl which is optionallymonosubstituted or polysubstituted by identical or differentsubstituents, preferred substituents which may be mentioned being:halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with ineach case 1 or 2 carbon atoms, nitro, halogenoalkyl, halogenoalkoxy andhalogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, such as, preferably, fluorine andchlorine atoms, the --CH═NOR² radical, and phenyl, phenoxy, benzyl andbenzyloxy, in each case optionally substituted by halogen and or alkylwith 1 or 2 carbon atoms;

X represents a nitrogen atom or the CH group;

Y represents a direct bond or the grouping --CH₂ --, --CH₂ CH₂ --,--OCH₂ --, --SCH₂ --, --CH═CH-- or --C.tbd.C--;

Z represents oxygen or the NOR² group; and

R² represents hydrogen, straight-chain or branched alkyl with 1 to 6carbon atoms or alkenyl or alkinyl with in each case 2 to 6 carbonatoms, or represents phenylalkyl which has 1 or 2 carbon atoms in thealkyl part and is optionally monosubstituted or polysubstituted byidentical or different substituents, possible substituents on the phenylbeing the substituents on the phenyl already mentioned for Ar; orrepresents cycloalkylmethyl which has 5 or 6 carbon atoms in thecycloalkyl part and is optionally mono-, di- or tri-substituted byidentical or different alkyl radicals with 1 to 3 carbon atoms.Particularly preferred compounds of the formula

(I) are those in which

R¹ represents straight-chain alkyl with 1 to 6 carbon atoms or thegrouping Ar--Y--;

Ar represents naphthyl, or represents phenyl which is optionally mono-,di- or tri-substituted by identical or different substituents,substituents which may be mentioned being: fluorine, chlorine, methyl,trifluoromethyl, trifluoromethoxy, trifluoromethylthio,methoximinomethyl, ethoximinomethyl and allyloximinomethyl, and phenyl,phenoxy, benzyl and benzyloxy, in each case optionally substituted bychlorine and/or methyl;

X represents a nitrogen atom or the CH group;

Y represents a direct bond or the grouping --CH₂ --, --CH₂ CH₂ --,--OCH₂ --, --SCH₂ --, --CH═CH-- or --C.tbd.C--; and

Z represents oxygen or the NOR² group, wherein

R² represents hydrogen, methyl, ethyl, n-propyl, n-butyl, allyl orpropargyl, or represents benzyl which is optionally mono-, di- ortri-substituted by identical or different substituents from the groupcomprising fluorine, chlorine, methyl, trifluoromethyl andtrifluoromethoxy, or represents cyclohexylmethyl which is optionallysubstituted by methyl or ethyl.

Addition products of acids and those hydroxyethylazole derivatives ofthe formula (I) in which the substituents R¹, X and Z have the meaningswhich have already been mentioned as preferred for these substituentsare also preferred compounds according to the invention.

Preferred acids which can be added on include hydrogen halide acids,such as, for example, hydrochloric acid and hydrobromic acid, inparticular hydrochloric acid, and furthermore phosphoric acid, nitricacid, monofunctional and bifunctional carboxylic acids andhydroxycarboxylic acids, such as, for example, acetic acid, maleic acid,succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,sorbic acid and lactic acid, and sulphonic acids, such as, for example,p-toluene-sulphonic acid and 1,5-naphthalenedisulphonic acid.

Addition products of salts of metals of main groups II to IV and ofsub-groups I and II and IV to VIII and those substitutedhydroxyethyl-azole derivatives of the formula (I) in which thesubstituents R¹, X and Z have the meanings which have already beenmentioned as preferred for these substituents are also preferredcompounds according to the invention.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel areparticularly preferred here. Possible anions of these salts are thosewhich are derived from acids which lead to physiologically acceptableaddition products. In this connection, particularly preferred acids ofthis type are the hydrogen halide acids, such as, for example,hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid,nitric acid and sulphuric acid.

The following compounds of the general formula (I) may be mentionedspecifically, in addition to the compounds mentioned in the preparationexamples: ##STR8## (wherein X represents either a nitrogen atom or theCH group):

    ______________________________________                                        R.sup.1           Z                                                           ______________________________________                                         ##STR9##         O                                                            ##STR10##        NOCH.sub.3                                                   ##STR11##        O                                                            ##STR12##        NOCH.sub.3                                                   ##STR13##        O                                                            ##STR14##        NOCH.sub.3                                                  CH.sub.3                                                                                         ##STR15##                                                  C.sub.2 H.sub.5                                                                                  ##STR16##                                                  C.sub.3 H.sub.7                                                                                  ##STR17##                                                  C.sub.4 H.sub.9                                                                                  ##STR18##                                                  C.sub.4 H.sub.9                                                                                  ##STR19##                                                  C.sub.4 H.sub.9                                                                                  ##STR20##                                                   ##STR21##        NOCH.sub.3                                                   ##STR22##        NOC.sub.2 H.sub.5                                            ##STR23##        NOC.sub.3 H.sub.7                                            ##STR24##        NOC.sub.4 H.sub.9                                            ##STR25##        NOCHCH.sub.2                                                 ##STR26##                                                                                       ##STR27##                                                   ##STR28##                                                                                       ##STR29##                                                   ##STR30##        NOCH.sub.3                                                   ##STR31##        NOCH.sub.2CHCH.sub.2                                         ##STR32##        NOCH.sub.3                                                   ##STR33##                                                                                       ##STR34##                                                   ##STR35##        NOC.sub.4 H.sub.9                                            ##STR36##        NOCH.sub.3                                                   ##STR37##        NOC.sub.2 H.sub.5                                            ##STR38##        NOC.sub.3 H.sub.7                                            ##STR39##        NOC.sub.4 H.sub.9                                            ##STR40##        NOCH.sub.2CHCH.sub.2                                         ##STR41##        NOCH.sub.3                                                   ##STR42##        NOCH.sub.3                                                  ______________________________________                                    

If, for example,1-(4-chlorophenoxy)-3-(1,3-dioxolan-2-yl)-3-methyl-2-(1,2,4-triazol-1-yl-methyl)-2-butanolin an ethanol/water mixture is used as the starting substance, thecourse of process (a) according to the invention can be represented bythe following equation: ##STR43##

If, for example,4-(4-chlorophenoxy)-2,2-dimethyl-3-hydroxy-3-(1,2,4-triazol-1-yl-methyl)-butanaland 0-methyl-hydroxylamine hydrochloride are used as starting substance,the course of process (b) according to the invention can be representedby the following equation: ##STR44##

If, for example,1-(4-chlorophenoxy)-3-hydroximino-methyl-3-methyl-2-(1,2,4-triazol-1-yl-methyl)-2-butanoland 4-chlorobenzyl chloride are used as starting substances, the courseof process (c) according to the invention can be represented by thefollowing equation: ##STR45##

If, for example,2-(2,4-dichlorophenyl)-2-(2-methoximinomethyl-2-propyl)-oxirane and1,2,4-triazole are used as starting substances, the course of process(d) according to the invention can be represented by the followingequation: ##STR46##

Formula (II) provides a general definition of thehydroxyethylazolyl-acetal derivatives to be used as starting substancesfor carrying out process (a) according to the invention. In thisformula, R¹ and X preferably have the meanings which have already beenmentioned as preferred for these substituents in connection with thedescription of the substances of the formula (I) according to theinvention. Z¹ and Z² preferably represent alkyl with 1 to 4 carbonatoms, such as, in particular, methyl, or, together with the oxygenatoms to which they are bonded, represented a dioxolane ring.

The hydroxyethylazolyl-acetal derivatives of the formula (II) are thesubject of German patent application No. P 3242222 filed Nov. 15, 1982now U.S. Pat. No. 4,622,333 and Application Ser. No. 547,807 filed Nov.1, 1983, now U.S. Pat. No. 4,639,462, corresponding to GermanApplication No. P 32 42 252 filed Nov. 15, 1982; or they can be obtainedby the processes described therein, by reacting oxiranes of the formula(VII) ##STR47## in which

R¹, Z¹ and Z² have the abovementioned meaning, with azoles of theformula (VI) in the presence of an inert organic solvent, such as, forexample, alcohols, and if appropriate in the presence of a base, suchas, for example, a sodium alcoholate or potassium hydroxide, attemperatures between 60° C. and 150° C.

The oxiranes of the formula (VII) are the subject of U.S. Pat. No.4,639,462, supra; or they can be obtained in a generally known manner,by reacting ketones of the formula (VIII) ##STR48## in which

R¹, Z¹ and Z² have the abovementioned meaning, either (α) withdimethyloxosulphonium methylidide of the formula (IX) ##STR49## in amanner which is known per se, in the presence of a diluent, such as, forexample, dimethylsulphoxide, at temperatures between 20° C. and 80° C.(in this context, compare the statements in J. Am. Chem. Soc. 87,1363-1364 (1965)), or (β) with trimethylsulphonium methyl-sulphate ofthe formula (X)

    [(CH.sub.3).sub.3 S.sup.(+) ]CH.sub.3 SO.sub.4.sup.(-)     (X)

in a manner which is known per se, in the presence of an inert organicsolvent, such as, for example, acetonitrile, and in the presence of abase, such as, for example, sodium methylate, at temperatures between 0°C. and 60° C., preferably at room temperature (compare also thestatements in Heterocycles 8, 397 (1777)).

If appropriate, the oxiranes of the formula (VII) thus obtained can befurther reacted directly, without being isolated.

Some of the ketones of the formula (VIII) are known (compare, forexample, J. Org. Chem. 32, 404 (1967)); or they are the subject ofApplication Ser. No. 503,102 filed June 10, 1983, now abandoned,corresponding to German Patent Application No. 32 24 130 filed June 29,1982, Application Ser. No. 503,220 filed June 10, 1983, now abandoned,corresponding to German Patent Application No. P 32 24 129 filed June30, 1982, and U.S. Pat. No. 4,622,333, supra; or they can be obtained ina known manner, for example by reacting 1-(N-morpholino)-isobutene ofthe formula (XI) ##STR50## with chlorides of the formula (XII)

    R.sup.1 --CO--Cl                                           (XII)

in which

R¹ has the abovementioned meaning, in the presence of a solvent, suchas, for example, diethyl ether, at temperatures between 20° C. and 120°C., and forming derivatives of the resulting keto derivatives of theformula (XIII) ##STR51## in which

R¹ has the abovementioned meaning, on the aldehyde group in thecustomary manner, such as, for example, by means of ethylene glycol inthe presence of an inert organic solvent, such as, for example, toluene,and in the presence of a strong acid as a catalyst, such as, forexample, p-toluenesulphonic acid, at temperatures between 80° C. and110° C.

In some cases, it proves to be advantageous to introduce the radical R¹or parts thereof only after the derivative has been formed on thealdehyde group (compare also the preparation examples).

The hydroxyethyl-azole derivatives of the formula (Ia) to be used asstarting substances in carrying out process (b) according to theinvention are compounds according to the invention.

Formula (III) provides a general definition of the hydroxylaminederivatives also to be used as starting substances for carrying outprocess (b) according to the invention. In this formula, R² preferablyhas the meanings which have already been mentioned as preferred for thissubstituent in connection with the description of the substances of theformula (I) according to the invention.

The hydroxylamine derivatives of the formula (III) are generally knowncompounds of organic chemistry.

The hydroxyethyl-azole derivatives of the formula (Ib) to be used asstarting substances in carrying out process (c) according to theinvention are compounds according to the invention.

Formula (IV) provides a general definition of the halides also to beused as starting substances for carrying out process (c) according tothe invention. In this formula, R³ preferably has those meanings whichhave already been mentioned as preferred for R², with the exception ofhydrogen, in connection with the description of the substances of theformula (I) according to the invention.

The halides of the formula (IV) are generally known compounds of organicchemistry.

Formula (V) provides a general definition of the oxiranes to be used asstarting substances in carrying out process (d) according to theinvention. In this formula, R¹ preferably has those meanings which havealready been mentioned as preferred for this substituent in connectionwith the description of the substances of the formula (I) according tothe invention, and R³ preferably has those meanings which have alreadybeen mentioned as preferred for R², with the exception of hydrogen, inconnection with the description of the substances of the formula (I)according to the invention.

The oxiranes of the formula (V) are not yet known; however, they can beobtained in a generally known manner by epoxidizing keto-oximederivatives of the formula (XIV) ##STR52## in which

R¹ and R² have the abovementioned meaning, by processes (α) or (β)described above.

The keto-oxime derivatives of the formula (XIV) are the subject ofapplication Ser. Nos. 547,807 now U.S. Pat. Nos. 4,622,333, 503,102 and503,220, supra; or they can be obtained in a known manner, for exampleby reacting 1-(N-morpholino)isobutene of the formula (XI) with chloridesof the formula (XII) in the presence of a solvent, such as, for example,diethyl ether, at temperatures between 20° C. and 120° C., and formingderivatives of the resulting keto derivatives of the formula (XIII) onthe aldehyde group in the customary manner by means of hydroxylaminederivatives of the formula (III), such as, for example,methoxyhydroxylamine hydrochloride, in the presence of an inert organicsolvent, such as, for example, ethanol, and in the presence of sodiumacetate at temperatures between 80° C. and 110° C. In some cases, itproves advantageous to introduce the radical R¹ or parts thereof onlyafter the derivative has been formed on the aldehyde group.

Formula (VI) provides a general definition of the azoles also to be usedas starting substances for carrying out process (d) according to theinvention. In this formula, X preferably represents the meanings whichhave already been mentioned as preferred for this substituent inconnection with the description of the substances of the formula (I)according to the invention. M preferably represents hydrogen, sodium orpotassium.

The azoles of the formula (VI) are generally known compounds of organicchemistry.

Process (a) according to the invention is carried out in the presence ofa mixture of water and a water-miscible, inert organic solvent.Preferred possible organic solvents are alcohols.

Possible acids for process (a) according to the invention are all theinorganic and organic acids which can customarily be used. Theseinclude, preferably, hydrochloric acid, sulphuric acid,p-toluenesulphonic acid and acetic acid.

The reaction temperatures can be varied within a substantial range incarrying out process (a) according to the invention. In general, thereaction is carried out at temperatures between 30° C. and 120° C.,preferably at the boiling point of the solvent used.

In carrying out process (a) according to the invention, 1 to 3 mols,preferably 2 mols, of acid are preferably employed per mol of thecompound of the formula (II). The end products are isolated in thegenerally customary manner.

Preferred possible diluents for process (b) according to the inventionare alcohols and water or mixtures of the two.

The reaction temperatures can be varied within a substantial range inprocess (b) according to the invention. In general, the reaction iscarried out between 20° C. and 120° C., preferably between 50° C. and100° C.

In carrying out process (b) according to the invention, 1 to 1.5 mols ofhydroxylamine derivative of the formula (III) are preferably employedper mol of the compound of the formula (Ia). The compounds of theformula (I) are isolated by customary methods.

According to a preferred embodiment of process (b), the hydroxylaminederivatives of the formula (III) are used in the form of their salts, inparticular as hydrochlorides, if appropriate in the presence of anacid-binding agent, such as, for example, sodium acetate (compare alsothe preparation examples).

Possible diluents for the reaction, according to the invention, inprocess (c) are inert organic solvents. These include, preferably,ethers, such as tetrahydrofuran and dioxane; aromatic hydrocarbons, suchas toluene and benzene; in individual cases also chlorinatedhydrocarbons, such as chloroform, methylene chloride or carbontetrachloride; and hexamethylphosphoric acid triamide, acid amides, suchas dimethylformamide, and sulphoxides, such as dimethylsulphoxide.

If appropriate, the reaction, according to the invention, in process (c)is carried out in the presence of a strong base. Strong bases include,preferably, alkali metal amides, hydrides, hydroxides and carbonates,such as, for example, sodium amide, carbonate, hydrocide or hydride andpotassium amide, carbonate, hydroxide or hydride, and quaternaryammonium hydroxides and phosphonium hydroxides, such as, for example,tetramethylammonium hydroxide, benzyltrimethyl-ammonium hydroxide ordibenzyl-dimethyl-ammonium hydroxide, and tetraphenylphosphoniumhydroxide or methyltriphenyl-phosphonium hydroxide.

The reaction temperatures can be varied within a substantial range inprocess (c). In general, the reaction is carried out between 20° C. and150° C., preferably at room temperature. In individual cases, it isadvantageous to carry out the reaction at the boiling point of thesolvent, for example between 60° C. and 100° C.

In carrying out process (c) according to the invention, 1 to 3 mols ofhalide of the formula (IV) are preferably employed per mol of thecompound of the formula (Ib). To isolate the end products, the reactionmixture is freed from the solvent, and water and an organic solvent areadded to the residue. The organic phase is separated off and worked upin the customary manner and the product is purified.

In a preferred embodiment of process (c), the reaction according to theinvention is carried out in a two-phase system, such as, for example,aqueous sodium hydroxide solution or potassium hydroxidesolution/toluene or methylene chloride, with addition of 0.01 to 1 molof a phase transfer catalyst, such as, for example, an ammonium orphosphonium compound, the alcoholates being formed in the organic phaseor at the interfaces and reacting with the halides in the organic phase.

Possible diluents for process (d) according to the invention are organicsolvents which are inert under the reaction conditions. These include,preferably: alcohols, such as, for example, ethanol, methoxyethanol orpropanol; ketones, such as, for example, 2-butanone; nitriles, such as,for example, acetonitrile; esters, such as, for example, ethyl acetate;ethers, such as, for example, dioxane; aromatic hydrocarbons, such as,for example, benzene and toluene; or amides, such as, for example,dimethylformamide.

Possible bases for process (d) according to the invention are all theinorganic and organic bases which can customarily be used. Theseinclude, preferably, alkali metal carbonates, such as, for example,sodium carbonate and potassium carbonate; alkali metal hydroxides, suchas, for example, sodium hydroxide; alkali metal alcoholates, such as,for example, sodium methylate and ethylate and potassium methylate andethylate; alkali metal hydrides, such as, for example, sodium hydride;and lower tertiary alkylamines, cycloalkylamines and aralkylamines, suchas, in particular, triethylamine.

The reaction temperatures can be varied within a substantial range incarrying out process (d) according to the invention. In general, thereaction is carried out at temperatures between 0° C. and 200° C.,preferably between 60° C. and 150° C.

In carrying out process (d) according to the invention, 1 to 2 mols ofazole and, if appropriate, 1 to 2 mols of base are preferably employedper mol of oxirane of the formula (V). The end products are isolated inthe generally customary manner.

Those acids which have already been mentioned as preferred acids inconnection with the description of the acid addition salts according tothe invention can preferably be used for the preparation of acidaddition salts of the compounds of general formula (I).

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the general formula (I) in asuitable inert solvent and adding the acid, for example hydrochloricacid, and they can be isolated in a known manner, for example byfiltration, and if appropriate purified by washing with an inert organicsolvent.

Those salts of metals which have already been described above canpreferably be used for the preparation of metal salt complexes of thecompounds of the general formula (I).

The metal salt complexes of the compounds of the general formula (I) canbe obtained in a simple manner by customary processes, thus, forexample, by dissolving the metal salt in alcohol, for example ethanol,and adding the solution to the compounds of the general formula (I). Themetal salt complexes can be isolated in a known manner, for example byfiltration, and if appropriate purified by recrystallization.

The active compounds according to the invention exhibit a powerfulmicrobicidal action and can be employed in practice for combatingundesired micro-organisms. The active compounds are suitable for use asplant protection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

As plant protection agents, the active compounds according to theinvention can be used with particularly good success for combatingCochliobolus sativus on barley and Venturia inaequalis on apples, andalso for combating powdery mildew, Septoria nodorum and Pyrenophorateres on cereals and Pyricularia oryzae and Pellicularia sasakii onrice.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, foams, pastes, soluble powders, granules, aerosols,suspension-emulsion concentrates, seed treatment powders, natural andsynthetic materials impregnated with active compound, very fine capsulesin polymeric substances and in coating compositions for seed, andformulations used with burning equipment, such as fumigating cartridges,fumigating cans, fumigating coils and the like, as well as ULV cold mistand warm mist formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid solid carriers, optionally with theuse of surface-active agents, that is, emulsifying agents and/ordispersing agents, and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strong polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussion Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyarinedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations or in the various use forms as a mixture with other knownactive compounds, such as fungicides, bactericides, insecticides,acaricides, nematicides, herbicides, bird repellents, growth factors,plant nutrients and agents for improved soil structure.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, emulsions, suspensions, powders, pastesand granules. They are used in the customary manner, for example bywatering, immersion, spraying, atomizing, misting, vaporizing,injecting, forming a slurry, brushing on, dusting, scattering, drydressing, moist dressing, wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrationsin the use form can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.0001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

PREPARATION EXAMPLES EXAMPLE 1 ##STR53##

(Process a)

15 ml of concentrated hydrochloric acid are added to 22.7 g (0.059 mol)of3-(1,3-dioxolan-2-yl)-2-(imidazol-1-yl-methyl)-3-methyl-1-(naphth-1-yl-oxy)-2-butanolin 150 ml of ethanol and 150 ml of water and the mixture is heated underreflux for 4 hours. The reaction mixture is then poured into saturated,aqueous sodium bicarbonate solution and extracted three times withmethylene chloride. The combined organic phases are washed with water,dried over sodium sulphate and concentrated. The residue is taken up inether/acetone and the product is filtered off with suction.

17.0 g (85.3% of theory) of2,2-dimethyl-3-hydroxy-3-(imidazol-1-yl-methyl)-4-(naphth-1-oxy)-butanalof melting point 147° C. are obtained.

Preparation of the starting substance: ##STR54##

A solution of 53.5 g (0.17 mol) of2-[2-(1,3-dioxolan-2-yl-prop-2-yl]-2-(naphth-1-yl-oxymethyl)-oxirane,12.8 g (0.188 mol) of imidazole and 1.3 g of potassium hydroxide in 350ml of absolute butanol is heated under reflux for 16 hours. The mixtureis allowed to cool to room temperature and 500 ml of methylene chlorideare added. The reaction mixture is washed twice with water. The organicphase is separated off, dried over sodium sulphate and concentrated. 350ml of diisopropyl ether and ethyl acetate are added to the residue. Theprecipitate which has separated out is filtered off with suction.

38.3 g (59.4% of theory) of3-(1,3-dioxolan-2-yl)-2-(imidazol-1-yl-methyl)-3-methyl-1-(naphth-1-yl-oxy)-2-butanolof melting point 126° C. are obtained. ##STR55##

67.2 g (0.6 mol) of potassium tert.-butylate are added in portions to131.1 g (0.596 mol) of trimethylsulphoxonium iodide in 120 ml ofabsolute dimethylformamide. The mixture is subsequently stirred at roomtemperature for 6 hours and a solution of 122 g (0.407 mol) of2-(1,3-dioxolan-2-yl)-prop-2-yl naphth-1-yl-oxymethyl ketone in 550 mlof absolute tetrahydrofuran is then added. The reaction mixture issubsequently stirred overnight at room temperature and concentrated, theresidue is taken up in methylene chloride and the mixture is washedtwice with water, dried over sodium sulphate and concentrated. Theresidue is extracted by stirring in petroleum ether and the product isfiltered off with suction.

107 g (83.7% of theory) of melting point 61° C. are obtained. ##STR56##

A solution of 141.5 g (0.735 mol) of1-chloro-3-(1,3-dioxolan-2-yl)-3-methyl-2-butanone, 105.9 g (0.835 mol)of 1-naphthol and 122 g (0.822 mol) of potassium carbonate in 1000 ml ofabsolute ethyl methyl ketone is heated under reflux for 16 hours. Themixture is allowed to cool to room temperature and is filtered. Thefiltrate is concentrated, methylene chloride is added to the residue andthe mixture is washed once with dilute sodium hydroxide solution andtwice with water, dried over sodium sulphate and concentrated. Theresidue is extracted by stirring in petroleum ether and the product isfiltered off with suction and dried.

122.6 g (55.6% of theory) of 2-(1,3-dioxolan-2-yl)-prop-2-ylnaphth-1-yl-oxymethyl ketone of melting point 69° C. are obtained.##STR57##

204 g (1.38 mol) of 4-chloro-2,2-dimethyl-3-ketobutanal are heated with93 g (1.5 mol) of ethylene glycol and 0.7 g of p-toluenesulphonic acidin 400 ml of methylene chloride for 3 hours, using a water separator.The organic phase is extracted with 150 ml of 5% strength sodiumhydroxide solution and then with 400 ml of water. The solvent isdistilled off and the residue is distilled under a waterpump vacuum.

211 g (79.8% of theory) of1-chloro-3-(1,3-dioxolan-2-yl)-3-methyl-butan-2-one of boiling point127° C. to 128° C./14 mbar are obtained. ##STR58##

210 g (1.5 mols) of 1-(N-morpholino)-isobutene are added dropwise, at 5°C. in the course of one hour, to 169 g (1.5 mols) of chloroacetylchloride dissolved in 350 ml of diethyl ether. When the addition hasended, the mixture is stirred for a further 3 hours, while cooling underreflux. The solution is poured onto 100 g of ice, the mixture is broughtto pH 5 with aqueous sodium bicarbonate solution and the ether phase isseparated off. The aqueous phase is extracted with 100 ml of diethylether, the organic phases are combined and dried over sodium sulphate,the solvent is distilled off and the residue is distilled under awaterpump vacuum.

136.4 g (61% of theory) of 4-chloro-2,2-dimethyl-3-keto-butanal ofboiling point 95° C. to 98° C./14 mbar are obtained.

EXAMPLE 2 ##STR59##

(Process b)

9 g (0.027 mol) of2,2-dimethyl-3-hydroxy-3-(imidazol-1-yl-methyl)-4-(naphth-1-oxy)-butanal(Example 1) and 2.2 g (0.027 mol) of 0-methyl-hydroxylaminehydrochloride are heated under reflux in 60 ml of ethanol for 16 hours.The reaction mixture is then concentrated, the residue is suspended inpetroleum ether and the product is filtered off with suction and dried.

9 g (90.7% of theory) of2-(imidazol-1-yl-methyl)-3-methoxyiminomethyl-3-methyl-1-(naphth-1-oxy)-2-butanolof melting point 177° C. to 178° C. are obtained.

The following compounds of the general formula (I) are obtained in ananalogous manner corresponding to the process description according tothe invention:

    __________________________________________________________________________     ##STR60##                                          (I)                       Example                               Melting point (°C.) or           No.  R.sup.1          X  Z            spectroscopic data                      __________________________________________________________________________          ##STR61##       N  O            107                                     4                                                                                   ##STR62##       N  NOCH.sub.3   144                                     5                                                                                   ##STR63##       N  O            Oil/IR.sub.CHCl.sbsb.3 : CHO = 1720                                           cm.sup.-1                               6                                                                                   ##STR64##       N  O            Oil/IR.sub.CHCl.sbsb.3 : CHO = 1722                                           cm.sup.-1                               7                                                                                   ##STR65##       N  O            105                                     8                                                                                   ##STR66##       N  O            136                                     9                                                                                   ##STR67##       N  O            119                                     10                                                                                  ##STR68##       N  NOCH.sub.3   121                                     11                                                                                  ##STR69##       N  O            147                                     12                                                                                  ##STR70##       N  NOCH.sub.3   151                                     13                                                                                  ##STR71##       N  NOCH.sub.3    93                                     14                                                                                  ##STR72##       N  O            147-151                                 15                                                                                  ##STR73##       N  NOCH.sub.3    96-101                                 16                                                                                  ##STR74##       CH O            127                                     17                                                                                  ##STR75##       N  NOCH.sub.3                                                                                  ##STR76##                              18                                                                                  ##STR77##       N  NOCH.sub.3                                                                                  ##STR78##                              19                                                                                  ##STR79##       N  O            Oil/IR.sub.CHCl.sbsb.3 : CHO = 1720                                           cm.sup.-1                               20                                                                                  ##STR80##       CH NOCH.sub. 3                                                                                 ##STR81##                              21                                                                                  ##STR82##       CH NOCH.sub.3                                                                                  ##STR83##                              22                                                                                  ##STR84##       N  NOCH.sub.3                                                                                  ##STR85##                              23                                                                                  ##STR86##       N  NOC.sub.4 H.sub.9                                                                           ##STR87##                              24                                                                                  ##STR88##       N  NOCH.sub.3   119                                     25                                                                                  ##STR89##       N  NOC.sub.2 H.sub.5                                                                          127-29                                  26                                                                                  ##STR90##       N  NOC.sub.4 H.sub.9n                                                                         138-40                                  27                                                                                  ##STR91##       N  NOCH.sub.2CHCH.sub.2                                                                       140-42                                  28                                                                                  ##STR92##       N                                                                                 ##STR93##   125-27                                  29                                                                                  ##STR94##       N                                                                                 ##STR95##    97                                     30                                                                                  ##STR96##       N                                                                                 ##STR97##   89-90                                   31                                                                                  ##STR98##       N                                                                                 ##STR99##    72                                     32                                                                                  ##STR100##      N  NOCH.sub.3   viscous oil                             33                                                                                  ##STR101##      N  NOCH.sub.2CHCH.sub.2                                                                       100-01                                  34   CH.sub.3         N                                                                                 ##STR102##  viscous oil                             35                                                                                  ##STR103##      N  NOCH.sub.3   55-57                                   36                                                                                  ##STR104##      N  NOCH.sub.2CHCH.sub.2                                                                        75                                     37                                                                                  ##STR105##      N  NOCH.sub.3    96-101                                 38                                                                                  ##STR106##      N  NOC.sub.3 H.sub.7n                                                                         112-14                                  39                                                                                  ##STR107##      N                                                                                 ##STR108##  130-33                                  40                                                                                  ##STR109##      N  NOC.sub.4 H.sub.9n                                                                         124-30                                  41   C.sub.3 H.sub.7 n-                                                                             N                                                                                 ##STR110##  viscous oil                             42   C.sub.3 H.sub.7 n-                                                                             N                                                                                 ##STR111##  viscous oil                             43   C.sub.2 H.sub.5  N                                                                                 ##STR112##  n.sub.D.sup.20  = 1 5456                44   C.sub.2 H.sub.5  N                                                                                 ##STR113##  viscous oil                             45   C.sub.4 H.sub.9 n-                                                                             N                                                                                 ##STR114##  n.sub.D.sup.20 = 1 5021                 46   C.sub.4 H.sub.9 n-                                                                             N                                                                                 ##STR115##  n.sub.D.sup.20 = 1 5353                 47   C.sub.4 H.sub.9 n-                                                                             N                                                                                 ##STR116##  n.sub.D.sup.20 = 1                      __________________________________________________________________________                                          5438                                

USE EXAMPLES

The substances shown below are used as comparison compounds in the useexamples which follow: ##STR117##

EXAMPLE: A

Cochliobolus sativus test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofCochliobolus sativus. The plants remain in an incubation cabinet for 48hours at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples: 7, 8, 3 and 4.

EXAMPLE B

Venturia test (apple)/protective/

Solvent: 4.7 parts of weight of acetone

Emulsifier: 0.3 parts of weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabinet at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples: 16 and 5.

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

What is claimed is:
 1. A hydroxyethyl-azole derivative of the formula##STR118## in which Ar represents naphthyl, or represents phenyl whichis unsubstituted, monosubstituted or disubstituted by identical ordifferent substituents selected from the group consisting of halogen;alkyl with 1 to 4 carbon atoms; halogenoalkyl having 1 to 2 carbon atomsand 1 to 5 identical or different halogen atoms; and phenyl, and Xrepresents a nitrogen atom or an addition product thereof with an acidor metal salt.
 2. A compound or addition product according to claim 1,in whichAr represents naphthyl, or represents phenyl which isunsubstituted or mono- or di-substituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and phenyl.
 3. A compound according to claim 1,wherein such compound is4-(4-biphenyloxy)-2,2-dimethyl-3-hydroxy-3-(1,2,4-triazol-1-yl-methyl)-butanalof the formula ##STR119## or an addition product thereof with an acid ormetal salt.
 4. A fungicidal composition comprising a fungicidallyeffective amount of a compound or addition product according to claim 1in admixture with an inert diluent.
 5. A method of combating fungi whichcomprises administering to such fungi or a fungus habitat a fungicidallyeffective amount of a compound or addition product according to claim 1.6. The method according to claim 5, wherein such compoundis4-(4-biphenyloxy)-2,2-dimethyl-3-hydroxy-3-(1,2,4-triazol-1-yl-methyl)-butanal.